Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
  • C09B67/0084—Dispersions of dyes
  • C09B67/0085—Non common dispersing agents
  • C09B67/0089—Non common dispersing agents non ionic dispersing agent, e.g. EO or PO addition products
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
  • C08G65/3311—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group
  • C08G65/3312—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group acyclic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
  • C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
  • C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0001—Post-treatment of organic pigments or dyes
  • C09B67/0022—Wet grinding of pigments
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
  • C09B67/0084—Dispersions of dyes
  • C09B67/0085—Non common dispersing agents
  • C09B67/009—Non common dispersing agents polymeric dispersing agent
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
  • C09B67/0092—Dyes in solid form
  • C09B67/0095—Process features in the making of granulates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
  • C08G2650/50—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing nitrogen, e.g. polyetheramines or Jeffamines(r)
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
  • C08G2650/58—Ethylene oxide or propylene oxide copolymers, e.g. pluronics
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0041—Optical brightening agents, organic pigments
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

• the present invention relates to pigment preparations, to the production of these pigment preparations and to their use for coloring macromolecular organic and inorganic materials.
• Liquid systems such as coatings, varnishes, emulsion paints and printing inks are customarily pigmented using pigment formulations comprising water, organic solvent or mixtures thereof.
• pigment formulations comprising water, organic solvent or mixtures thereof.
• anionic, cationic, nonionic or amphoteric dispersants these pigment formulations generally have to be additized with further auxiliaries, such as dried-crust inhibitors, freeze resistance enhancers, thickeners and anti-skinners, for stabilization.
• WO-A 03/64540, WO-A 03/66743, WO-A 04/00903, WO-A 04/29159, WO-A 04/46251, WO-A 04/50770 and also WO-A 06/084849, WO-A 06/084861 and WO-A 00/47681 all describe pigment preparations comprising nonionic surface-active additives based on polyethers and/or anionic water-soluble surface-active additives based on acidic esters of these polyethers, on polymers of ethylenically unsaturated carboxylic acids and/or on polyurethanes and also fillers, and being notable for this stir-in behavior.
• Prior art pigment preparations do have adequate stir-in characteristics for aqueous systems, but are not universally useful in all aqueous systems. It is specifically in aqueous vinyl acetate dispersions that these products exhibit infirmities. Nor are these products very suitable for use in solvent-containing systems.
• the present invention also provides a process for producing a preparation of the present invention, which comprises wet-comminuting the component (A) in an aqueous suspension comprising some or all of the additive (B) and optionally (D) either in the presence of the additive (C) or subsequently adding the additive (C) and optionally (D) and then drying the suspension, if appropriate after addition of the remaining amount of additive (B) and optionally (D).
• the present invention further provides a process for coloring macromolecular organic and inorganic materials, which comprises incorporating the preparation according to the present invention into these materials by stirring or shaking.
• the materials may comprise particularly materials which are varnishes, paints, printing inks, liquid inks or coating systems comprising water, organic solvents or mixtures of water and organic solvents as liquid phase.
• the present invention further provides a process for coloring macromolecular organic and inorganic materials using color-mixing systems, which comprises using a preparation of the present invention as mixing components.
• the pigment preparations of the present invention comprise the pigment component (A), the nonionic water-soluble surface-active additive (B) and the nonionic surface-active additive (C) as essential constituents, with the components (B) and (C) each being based on polyethers.
• further additives other than those of components (B) and (C) can be present to form the component (D). It will be appreciated that all the constituents sum to 100% by weight of the preparation.
• the sum total of the weight fractions of components (B) and (C) based on the total weight of the preparation is in the range from 10% by weight to 30% by weight and more preferably in the range from 15% by weight to 30% by weight.
• Component (A) in the pigment preparations of the present invention may comprise organic or inorganic pigments. It will be appreciated that the pigment preparations may also comprise mixtures of various organic or various inorganic pigments or mixtures of organic and inorganic pigments. The same logic applies to fillers and mixtures of pigment(s) and filler(s).
• the component (A) comprises at least one pigment and optionally at least one pigment synergist. It is similarly preferable for the component (A) to comprise at least one filler.
• the pigments are typically present in finely divided form.
• the pigments accordingly typically have average particle sizes in the range from 0.1 to 5 ⁇ m.
• Organic pigments typically comprise organic color and black pigments.
• Inorganic pigments may likewise comprise color pigments (chromatic, black and white pigments) and also luster pigments and the inorganic pigments typically used as fillers.
• Suitable inorganic color pigments are:
• inorganic pigments typically used as fillers are transparent silicon dioxide, ground quartz, aluminum oxide, aluminum hydroxide, natural micas, natural and precipitated chalk and barium sulfate.
• Luster pigments are platelet-shaped pigments having a monophasic or polyphasic construction whose color play is marked by the interplay of interference, reflection and absorption phenomena. Examples are aluminum platelets and aluminum, iron oxide and mica platelets bearing one or more coats, especially of metal oxides.
• the pigment derivatives recited hereinbelow are particularly useful as pigment synergists which can combine with one or more pigments, in particular organic pigments, to form the pigment component (A).
• the component (A) comprises at least one pigment synergist as well as at least one pigment.
• the fraction of the total weight of the preparation of the present invention which is attributable to a pigment synergist is preferably in the range from 0.01% by weight to 5% by weight and more preferably in the range from 0.1% by weight to 3% by weight.
• Pigment synergists preferably comprise pigment derivatives of formula I
• the pigment derivatives I are based on an organic pigment's core structure P which is functionalized by sulfonic acid and/or carboxylic acid groups which are attached to the core structure either directly or via bridging elements.
• core structure shall comprehend the pigments themselves and also their precursors. Pigment precursors come into consideration in the case of polycyclic pigments in particular. They have the ring scaffold of the pigment, but the pigment's full substitution pattern is not present and/or functionalizations are missing.
• Perylene-3,4-dicarboximides may be mentioned as an example of a precursor to perylene pigments based on perylene-3,4,9,10-tetracarboxylic acids and their diimides.
• pigment core structures selected from the group consisting of the quinophthalone, perylene and phthalocyanine pigments are particularly preferred.
• pigment core structures selected from the group consisting of the quinophthalone and phthalocyanine pigments which are very particularly preferred.
• Quinophthalone-based pigment derivatives I are particularly useful for combination with yellow, orange and red pigments
• phthalocyanine-based pigment derivatives I are especially useful for combination with blue, green, violet and black pigments.
• the sulfonic acid and/or carboxylic acid groups X and Y are directly attached to the pigment core structure P in the pigment derivatives I, i.e., T 1 and B 1 and also T 2 and B 2 are all preferably a chemical bond.
• T 1 and T 2 may also be bridging moieties of the formula —CONR 1 — or —SO 2 NR 1 — (R 1 : hydrogen; C 1 -C 4 -alkyl; naphthyl or especially phenyl, which may each be substituted by C 1 -C 18 -alkyl but each preferably unsubstituted).
• R 1 hydrogen; C 1 -C 4 -alkyl; naphthyl or especially phenyl, which may each be substituted by C 1 -C 18 -alkyl but each preferably unsubstituted.
• particularly useful bridging moieties T 1 and T 2 are —CONH—, SO 2 NH—, —CON(CH 3 )— and —SO 2 N(CH 3 )—.
• B 1 and B 2 may be branched or unbranched C 1 -C 8 -alkylene radicals or phenylene radicals. Examples are: methylene, 1,1- and 1,2-ethylene, 1,1-, 1,2- and 1,3-propylene and 1,4-, 1,3- and 1,2-phenylene.
• Suitable combinations of the bridging moieties T and B are —CONH—CH 2 —, —CON(CH 3 )—CH 2 —, —CONH—C 2 H 4 —, —CONH—CH(CH 3 )—, —SO 2 NH—CH 2 —, —SO 2 N(CH 3 )—CH 2 —, —SO 2 NH—C 2 H 4 —, —SO 2 NH—CH(CH 3 )—, —CONH-1, 4-C 6 H 4 — and —SO 2 NH-1, 4-C 6 H 4 —.
• the sulfonic acid and/or carboxylic acid groups X and Y may each be present as a free acid or as a salt (Ka + : Li + , Na + , K + or N + R 2 R 3 R 4 R 5 ).
• the ammonium salts may be formed of unsubstituted ammonium ions, but preferably at least one of R 2 , R 3 , R 4 and R 5 is other than hydrogen.
• Suitable aliphatic radicals R 2 , R 3 , R 4 and R 5 are C 1 -C 30 -alkyl and C 3 -C 30 -alkenyl radicals which may each be branched or unbranched and C 5 -C 6 -cycloalkyl radicals which may be substituted by C 1 -C 24 -alkyl and preferably by C 1 -C 18 -alkyl.
• Useful aromatic radicals are phenyl and naphthyl which may each be substituted by C 1 -C 24 -alkyl or by C 2 -C 24 -alkenyl, especially by C 1 -C 18 -alkyl or C 2 -C 18 -alkenyl.
• the radicals R 2 , R 3 , R 4 and R 5 may also be polyalkyleneoxy radicals of the formula —[CHR 6 —CHR 7 —O] x —R 8 (R 6 , R 7 and R 8 : independently hydrogen, C 1 -C 6 -alkyl; x ⁇ 1).
• the radicals can be homopolymeric, i.e. for example pure polyethyleneoxy or pure polypropyleneoxy radicals, or copolymeric radicals which comprise various alkyleneoxy units especially as blocks or else randomly, for example polyethyleneoxy-polypropyleneoxy radicals.
• ammonium salts are mono-C 8 -C 30 -alkyl- or -alkenylammonium salts, e.g. lauryl, stearyl, oleyl or tallow alkylammonium salts, and also quaternized ammonium salts which contain from 24 to 42 carbon atoms in total, provided at least one and preferably two of the alkyl and/or alkenyl radicals have at least 8, preferably 12 and more preferably from 12 to 20 carbon atoms, e.g. dimethyldidodecyl-, dimethyldioleyl- and dimethyldistearylammonium salts.
• the sulfonic acid and/or carboxylic acid groups X and Y are not present in free form in the pigment derivatives I.
• the formation of the salt and especially the formation of the sodium salt generally takes place in the course of the production of the pigment preparation, which in this case preferably comprises a neutralizing step.
• a nonionic surface-active additive is used that has a basic site, for example a nitrogen atom, the acid groups may of course also react with this additive to form a salt.
• the preferred sodium and/or ammonium salts should at least constitute a high fraction of these mixtures.
• the pigment derivatives I may comprise from 1 to 4 acid groups.
• the pigment derivatives I can constitute random mixtures of molecules having various degrees of substitution so that the mean value of the sum m+n can be a fractional number.
• the pigment derivatives I comprise sulfonic acid groups only.
• a degree of substitution (m+n) in the range from 1 to 3 and especially in the range from 1 to 2 will prove particularly advantageous.
• m is preferably in the range from 1 to 1.8 and n in the range from 0 to 0.2.
• Ka + and m+n have the meanings defined at the outset, although Ka is preferably Na + or N + R 2 R 3 R 4 R 5 (especially with the above-recited preferred combinations of the radicals R 2 to R 5 ).
• the sum m+n is in particular 1 in the case of the compounds Ia and Ic, and the sulfonic acid group is preferably in position 6 in the case of the compounds Ia and preferably in position 9 in the case of the compounds Ic.
• Rings A and A′ in the formula Ia may be the same or different and may each be substituted by from 1 to 4 chlorine and/or fluorine atoms.
• each ring bears 4 chlorine atoms.
• D represents —O— or —NR 9 —, where R 9 is hydrogen, C 1 -C 4 -alkyl or unsubstituted or C 1 -C 4 -alkyl-substituted, C 1 -C 4 -alkoxy- and/or phenylazo-substituted phenyl.
• R 9 is hydrogen, methyl, 4-ethoxyphenyl, 3,5-dimethylphenyl or 4-phenylazophenyl.
• Very particularly preferred pigment derivatives Ia and Ib are those where the symbols each have the preferred meanings, in which connection the pigment derivatives Ia may preferably be present in the form of sodium salts and the pigment derivatives Ib may be present not only as sodium but also as ammonium salts.
• Organic core structures for pigments further include azo, diketopyrrolopyrrole, metal complexes, quinacridones, isoindoline and isoindolinones.
• the pigment derivatives I are known and are obtainable by following known methods.
• component (B) and (C) differ in their chemical construction.
• Component (B) is based on ethylene oxide polyethers or ethylene oxide (EO)-propylene oxide (PO) copolymers having terminal ethylene oxide units and component (C) is based on PO polyethers or EO-PO copolymers having terminal propylene oxide units.
• component (C) may include water-insoluble EO adducts.
• component (B) is notable for its solubility in water, while component (C) is characterized by its water insolubility and/or end group hydrophobicization (compared with EO).
• Component (B) thus is water-soluble, while component (C) can be water-soluble or water-insoluble.
• materials having an HLB value of >10 can be regarded as water-soluble and materials having an HLB value of ⁇ 10 can be regarded as water-insoluble.
• the HLB value is the ratio of the amount of ethylene oxide to the total amount ⁇ 20.
• the HLB value is defined by the formula
• H ⁇ ⁇ L ⁇ ⁇ B 20 ⁇ ( 1 - M L M G ) , where M L is the molecular weight of the lipophilic moieties and M G is the total weight. Further details can be found in H.-D. Dörfer, Grenzfest and kolloid-disperse Systeme, Springer Verlag 2002, chapter 9.3 “Physical properties and effects of surfactants”.
• Component (B) comprises at least one nonionic water-soluble surface-active additive selected from the group consisting of ethylene oxide homopolymers; ethylene oxide-propylene oxide block copolymers where the terminal blocks consist of ethylene oxide units; ethylene oxide adducts on mono- or bifunctional amines or alcohols where the length of the ethylene oxide chain is chosen such that the adduct is water-soluble; and ethylene oxide-propylene oxide block copolymer adducts on mono- or bifunctional amines or alcohols where the terminal block consists of ethylene oxide units.
• nonionic water-soluble surface-active additive selected from the group consisting of ethylene oxide homopolymers; ethylene oxide-propylene oxide block copolymers where the terminal blocks consist of ethylene oxide units; ethylene oxide adducts on mono- or bifunctional amines or alcohols where the length of the ethylene oxide chain is chosen such that the adduct is water-soluble; and ethylene oxide-propylene oxide block copolymer a
• the component (B) comprises at least one of the additives which is selected from the group consisting of ethylene oxide-propylene oxide block copolymers where the terminal blocks consist of ethylene oxide units; ethylene oxide adducts on bifunctional amines where the length of the ethylene oxide chain is chosen such that the adduct is water-soluble; ethylene oxide-propylene oxide block copolymer adducts on bifunctional amines where the terminal block consists of ethylene oxide units; ethylene oxide adducts on monofunctional alcohols where the length of the ethylene oxide chain is chosen such that the adduct is water-soluble; and ethylene oxide-propylene oxide block copolymer adducts on monofunctional alcohols where the terminal block consists of ethylene oxide units.
• the additives which is selected from the group consisting of ethylene oxide-propylene oxide block copolymers where the terminal blocks consist of ethylene oxide units; ethylene oxide adducts on bifunctional amines where the length of the ethylene oxide chain is chosen
• component (B) comprises an ethylene oxide homopolymer
• the latter preferably has a molecular weight in the range from 400 g/mol to 10 000 g/mol.
• component (B) comprises an ethylene oxide (EO)-propylene oxide block (PO) copolymer having terminal blocks of ethylene oxide units
• these blocks preferably include the order EO-PO-EO or EO-PO-EO-PO-EO and more preferably EO-PO-EO.
• the molecular weight of such a copolymer is preferably in the range from 1000 g/mol to 20 000 g/mol.
• the molar fraction which the ethylene oxide units contribute to the total amount of the coploymer is preferably at least 30 mol % and more preferably in the range from 40 mol % to 60 mol %.
• component (B) comprises an ethylene oxide adduct on mono- or bifunctional amines or alcohols having a length of ethylene oxide chain chosen such that the adduct is water-soluble
• this adduct preferably includes a number of ethylene oxide units in the range from 10 units to 100 units.
• the monofunctional alcohol and monofunctional amine preferably comprises a branched or unbranched alkanol/amine having 10 to 20 carbon atoms, and the alkanol/amine is preferably a primary alcohol or primary amine respectively.
• a bifunctional alcohol preferably comprises glycol, 1,2-propanediol or 1,3-propanediol.
• a bifunctional amine preferably comprises ethylenediamine, 1,3-propylenediamine or 1,4-butylenediamine.
• the molecular weight of the adduct with bifunctional amines or alcohols is preferably in the range from 1000 g/mol to 40 000 g/mol.
• component (B) comprises an ethylene oxide-propylene oxide block copolymer adduct on mono- or bifunctional amines or alcohols having a terminal block of ethylene oxide units
• this adduct preferably includes just one propylene oxide and one ethylene oxide block.
• the number of ethylene oxide units is preferably in the range from 10 to 1000 units and more preferably in the range from 10 to 750 units.
• the number of propylene oxide units is preferably in the range from 1 to 250 units and more preferably in the range from 10 to 200 units. It is also possible for there to be just small fractions of propylene oxide units, for example 1 to 10 units, preferably 1 to 3 units and, in particular, 1 propylene oxide unit.
• the monofunctional alcohol and monofunctional amine preferably comprises a branched or unbranched alkanol/amine having 10 to 20 carbon atoms, and the alkanol/amine is preferably a primary alcohol or primary amine respectively.
• a bifunctional alcohol preferably comprises glycol, 1,2-propanediol or 1,3-propanediol.
• a bifunctional amine preferably comprises ethylenediamine, 1,3-propylenediamine or 1,4-butylenediamine.
• the molecular weight of the adduct with bifunctional amines or alcohols is preferably in the range from 1000 g/mol to 40 000 g/mol.
• Component (C) comprises at least one surface-active additive selected from the group consisting of propylene oxide homopolymers; ethylene oxide-propylene oxide block copolymers where the terminal blocks consist of propylene oxide units; ethylene oxide adducts on mono- or bifunctional amines or alcohols where the length of the ethylene oxide chain is chosen such that the adduct is water-insoluble; and ethylene oxide-propylene oxide block copolymer adducts on mono- or bifunctional amines or alcohols where the terminal block consists of propylene oxide units.
• the component (C) comprises at least one of the additives which is selected from the group consisting of ethylene oxide-propylene oxide block copolymers where the terminal blocks consist of propylene oxide units; ethylene oxide-propylene oxide block copolymer adducts on bifunctional amines where the terminal block consists of propylene oxide units.
• component (C) comprises a propylene oxide homopolymer
• the latter preferably has a molecular weight in the range from 400 g/mol to 10 000 g/mol.
• component (C) comprises an ethylene oxide-propylene oxide block copolymer having terminal blocks of propylene oxide units
• these blocks preferably have the sequence PO-EO-PO or PO-EO-PO-EO-PO and more preferably PO-EO-PO.
• the molecular weight of such a copolymer is in the range from 1000 g/mol to 10 000 g/mol and more preferably in the range from 1000 g/mol to 5000 g/mol.
• the number of propylene oxide units in the copolymer is preferably in the range from 10 to 100 units and the number of ethylene oxide units is preferably in the range from 1 to 100 units and more preferably in the range from 1 to 75 units.
• component (C) comprises an ethylene oxide adduct on mono- or bifunctional amines or alcohols having a length of ethylene oxide chain chosen such that the adduct is water-insoluble, the number of ethylene oxide units is preferably less than 10.
• the monofunctional alcohol and monofunctional amine preferably comprises a branched or unbranched alkanol/amine having 10 to 20 carbon atoms, and the alkanol/amine is preferably a primary alcohol or primary amine respectively.
• a bifunctional alcohol preferably comprises glycol, 1,2-propanediol or 1,3-propanediol.
• a bifunctional amine preferably comprises ethylenediamine, 1,3-propylenediamine or 1,4-butylenediamine.
• component (C) comprises an ethylene oxide-propylene oxide block copolymer adduct on mono- or bifunctional amines or alcohols having a terminal block of propylene oxide units
• this adduct preferably includes just one propylene oxide and one ethylene oxide block.
• the monofunctional alcohol and monofunctional amine preferably comprises a branched or unbranched alkanol/amine having 10 to 20 carbon atoms, and the alkanol/amine is preferably a primary alcohol or primary amine respectively.
• a bifunctional alcohol preferably comprises glycol, 1,2-propanediol or 1,3-propanediol.
• a bifunctional amine preferably comprises ethylenediamine, 1,3-propylenediamine or 1,4-butylenediamine.
• the molecular weight of the adduct with bifunctional amines or alcohols is preferably in the range from 1000 g/mol to 40 000 g/mol, more preferably in the range from 1000 g/mol to 30 000 g/mol.
• the number of propylene oxide units in the copolymer is preferably in the range from 10 to 100 units, and the number of ethylene oxide units is preferably in the range from 1 to 100 units and more preferably in the range from 1 to 75 units.
• solubility in solvents is achieved by reducing the solubility in water.
• Water-insoluble additives can thus be dispersed in water in the presence of a water-soluble additive.
• Water solubility/hydrophobicization is thus controllable for example by hydrophobic propylene oxide blocks being in the terminal or middle position, or by reducing the number of ethylene oxide units in adducts in order that their solubility in water may be reduced.
• the compounds or components (B) and (C) can be constructed as described above, in which case their distinction due to the water solubility or terminal position of PO groups can be achieved by the abovementioned measures for example.
• products having fewer than 10, preferably fewer than 8 and more preferably fewer than 6 ethylene oxide units are water-insoluble.
• Terminal propylene oxide units reduce solubilities in water, and/or constitute more hydrophobic end groups. Water solubilities are discernible from the technical data leaflets of the individual products.
• the polyethers comprise EO and/or PO polyalkylene oxides or corresponding reaction products with alcohols and amines.
• alkylene oxide or EO
• PO shall also comprehend aryl-substituted alkylene oxide, especially phenyl-substituted ethylene oxide.
• alkylene oxide or EO, PO shall not include any such substituents.
• the adducts on mono- or bifunctional alcohols or amines preferably comprise the abovementioned alcohols and amines.
• Suitable aliphatic alcohols comprise in general from 6 to 26 carbon atoms and preferably from 8 to 18 carbon atoms and can have an unbranched, branched or cyclic structure. Examples are octanol, nonanol, decanol, isodecanol, undecanol, dodecanol, 2-butyloctanol, tridecanol, isotridecanol, tetradecanol, pentadecanol, hexadecanol (cetyl alcohol), 2-hexyldecanol, heptadecanol, octadecanol (stearyl alcohol), 2-heptylundecanol, 2-octyldecanol, 2-nonyltridecanol, 2-decyltetradecanol, oleyl alcohol and 9-octadecenol and also mixtures of these alcohols, such as C 8 /C 10 , C
• the alkylene oxide adducts with these alcohols typically have average molecular weights M n from 200 to 5000, in particular from 400 to 2000.
• aromatic alcohols include not only ⁇ - and ⁇ -naphthol and their C 1 -C 4 -alkyl derivatives but also in particular phenol and its C 1 -C 12 -alkyl derivatives, such as hexylphenol, heptylphenol, octylphenol, nonylphenol, isononylphenol, undecylphenol, dodecylphenol, di- and tributylphenol and dinonylphenol.
• Suitable aliphatic amines correspond to the abovementioned aliphatic alcohols. Again of particular importance here are the saturated and unsaturated fatty amines which preferably have from 14 to 20 carbon atoms. Examples of suitable aromatic amines are aniline and its derivatives.
• bifunctional amines there may be used for example amines having two amine groups and conforming in particular to the formula H 2 N—(R—NR 1 ) 2 —H (R: C 2 -C 6 -alkylene; R 1 : hydrogen or C 1 -C 6 -alkyl).
• R C 2 -C 6 -alkylene
• R 1 hydrogen or C 1 -C 6 -alkyl
• Specific examples are: ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,3-propylenediamine, dipropylenetriamine, 3-amino-1-ethyleneaminopropane, hexamethylenediamine, dihexamethylenetriamine, 1,6-bis(3-aminopropylamino)hexane and N-methyldipropylenetriamine.
• bifunctional alcohols there may be mentioned by way of example C 2 -C 6 -alkylene glycols and the corresponding di- and polyalkylene glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, dipropylene glycol and polyethylene glycol.
• alkylene oxide block copolymers are known and are commercially available for example under the names of Tetronic® (water-soluble and water-insoluble), Pluronic® (water-soluble and water-insoluble) (BASF) and Synperonic® (Uniqema).
• the pigment preparations of the present invention comprise at least 60% by weight, preferably 60% to 90% by weight and more preferably 70% to 85% by weight of component (A), 1% to 39% by weight and preferably 5% to 30% by weight of component (B) and 1% to 39% by weight, preferably 1% to 25% by weight, and especially 1% to 20% by weight of component (C), all based on the total weight of the preparation.
• the preparation of the present invention may further comprise further constituents (D). These comprise a fraction ranging from 0% by weight to 10% by weight based on the total weight of the preparation. These are thus present or not present, and if present their proportion is preferably in the range from 0.1% by weight to 10% by weight, more preferably in the range from 0.5% by weight to 7.5% by weight and even more preferably in the range from 1% by weight to 5% by weight.
• D further constituents
• Antioxidants may be concerned here for example.
• antioxidants examples include the known classes of sterically hindered phenols, aromatic amines, thiosynergists, phosphites and phosphonites and sterically hindered amines.
• Antioxidants based on sterically hindered phenols comprise as essential building block a phenol substituted by at least one tert-butyl group in the ortho position, in particular by tert-butyl groups in both ortho positions, relative to the OH group.
• Most known products comprise two or more of these building blocks, which are bonded together via various bridging members.
• Antioxidants based on aromatic amines comprise in the main diarylamines, amine-ketone condensation products, for example aniline-acetone condensates and substituted p-phenylenediamines.
• thiosynergists are the metal salts of dialkyldithiocarbamic acids, zinc dialkyldithiophosphates and esters (particularly dilauryl, dimyristyl and distearyl esters) of thiodipropionic acid.
• Antioxidants based on phosphites and phosphonites typically comprise esters of the corresponding acids of phosphorus with alkyl-substituted, more particularly tert-butyl-substituted, phenols.
• Antioxidants based on sterically hindered amines comprise as essential building block a 2,6-dialkyl-substituted, more particularly a -dimethyl-substituted, piperidine which is linked in the 4-position via a wide variety of bridging members to further piperidine building blocks.
• Antioxidants are common knowledge and obtainable for example under the names of Irganox®, Irgaphos®, Chimassorb® and Irgastab® (Ciba), Topanol® (ICI), Hostanox® (Clariant) and Goodrite® (Goodyear).
• the antioxidant content is generally in the range from 0.1% to 5% by weight and particularly in the range from 0.1% to 2% by weight based on the total weight of the preparation.
• the preparation may further comprise small amounts of defoamers (0.01% to 0.2% by weight based on the total weight of the preparation for example from Tego, Byk, Borchers) and biocides (0.01% to 0.5% by weight based on the total weight of the preparation for example from Thor, Rohm & Haas).
• the preparation may further comprise thickeners (preferably 0.01% by weight to 2% by weight, if present, based on the total weight of the preparation, for example from Coatex, BASF, Tego, Aqualon).
• component (D) there may be mentioned for example anionic dispersants as described for example in WO-A 04/046251 or polyurethane-based dispersants as described in WO-A 06/084861.
• the preparation of the present invention is advantageously obtainable by the production process which is likewise in accordance with the present invention, by wet-comminuting the component (A) in an aqueous suspension comprising some or all of the additive (B) and optionally (D) either in the presence of the additive (C) or subsequently adding the additive (C) and optionally (D) and then drying the suspension, if appropriate after addition of the remaining amount of additive (B) and optionally (D).
• Component (A) can be used in the process of the present invention as a dry powder or in the form of a presscake.
• component (A) is used in the form of a conditioned product, i.e., the primary particle size of the pigment has already been adjusted to the value desired for the application.
• Pigment conditioning is particularly advisable in the case of organic pigments, since the as-synthesized crude product of a pigment synthesis is generally not directly suitable for use.
• inorganic pigments for example oxide and bismuth vanadate pigments
• adjustment of the primary particle size can also take place in the course of pigment synthesis, so that the as-synthesized pigment suspensions can be used directly in the process of the present invention.
• the conditioned pigment (A) typically reagglomerates in the course of drying or on the filter assembly, it is subjected to wet comminution, for example grinding in a stirred media mill, in aqueous suspension.
• the wet comminution should be carried out in the presence of some or all of the additive (B) which is present in the final pigment preparation, and it is preferable to add the entire amount of additive (B) before the wet-comminuting operation.
• Additive (C) can be added before, during or after the wet-comminuting operation.
• the additive (D) can be added together with (B) or (C).
• the particle size of the pigment preparations of the present invention can be controlled to a specifically targeted value.
• Spray and fluidized bed granulation may yield coarsely divided granules having average particle sizes from 50 to 5000 ⁇ m, and particularly from 100 to 1000 ⁇ m.
• Spray drying typically yields granules having average particle sizes ⁇ 20 ⁇ m.
• Finely divided preparations are obtainable by drying in a paddle dryer and by evaporation with subsequent grinding.
• the pigment preparations of the present invention are in granule form.
• Spray granulation is preferably carried out in a spray tower using a one-material nozzle.
• the suspension is spray dispensed in the form of relatively large drops, and the water evaporates.
• the additives (B) and (C) melt at the drying temperatures and so lead to the formation of a substantially spherical granule having a particularly smooth surface (BET values generally ⁇ 15 m 2 /g and particularly ⁇ 10 m 2 /g.
• a preferred process of spray granulation comprises the following steps:
• the preparation of the present invention comprises granules having an average particle size in the range from 50 to 5000 ⁇ m and a BET surface area of ⁇ 15 m 2 /g.
• the gas inlet temperature in the spray tower is generally in the range from 180 to 300° C. and preferably in the range from 150 to 300° C.
• the gas outlet temperature is generally in the range from 70 to 150° C. and preferably in the range from 70 to 130° C.
• the residual moisture content of the granular pigment obtained is generally ⁇ 2% by weight.
• the pigment preparations of the present invention are notable in use for their excellent color properties which are comparable to those of liquid pigment formulations, especially with regard to color strength, brilliance, hue and hiding power, and in particular for their stir-in characteristics, ie they can be dispersed in application media with a minimal input of energy, simply by stirring or shaking. This applies in particular to the coarsely divided pigment granules, which constitute the preferred embodiment of the pigment preparations of the present invention.
• the pigment preparations of the present invention additionally have the following advantages: They have a higher pigment content. Whereas liquid formulations tend to change viscosity during storage and have to be admixed with preservatives and agents for enhancing the resistance to freezing and/or drying out (crusting), the pigment preparations of the present invention exhibit very good stability in storage. They are both economically and ecologically advantageous with regard to packaging, storage and transportation. Since they are solvent free, they are more flexible in use.
• the pigment preparations of the present invention which are in granule form are notable for excellent attrition resistance, a minimal tendency to compact or clump, uniform particle size distribution, good pourability, flowability and meterability and also dustlessness in handling and application.
• the pigment preparations of the present invention are very useful for pigmenting macromolecular organic and inorganic materials of any kind.
• Liquid application media in this context can also be purely aqueous; comprise mixtures of water and organic solvents, for example alcohols; or be based exclusively on organic solvents, such as alcohols, glycol ethers, ketones, eg methyl ethyl ketone, amides, eg N-methylpyrrolidone and dimethylformamide, esters, eg ethyl acetate, butyl acetate and methoxypropyl acetate, or aromatic or aliphatic hydrocarbons, eg xylene, mineral oil and mineral spirits.
• Examples of materials which can be pigmented with the pigment preparations of the present invention include: coatings, for example architectural coatings, industrial coatings, automotive coatings, radiation-curable coatings; paints, including paints for building exteriors and building interiors, for example wood paints, lime washes, distempers, emulsion paints; printing inks, for example offset printing inks, flexographic printing inks, toluene gravure printing inks, textile printing inks, radiation-curable printing inks; liquid inks, including inkjet inks; color filters; building materials (water is typically added only after building material and pigment preparation have been dry mixed), for example silicate render systems, cement, concrete, mortar, gypsum; bitumen, caulks; cellulosic materials, for example paper, paperboard, cardboard, wood and woodbase, which can each be coated or otherwise finished; adhesives; film-forming polymeric protective colloids as used for example in the pharmaceutical industry; cosmetic articles; detergents.
• coatings for example
• the pigment preparations of the present invention are particularly useful as mixing components in color-mixing or -matching systems. Owing to their stir-in characteristics, they can be used directly as a solid for this purpose. If desired, however, they can also be first converted into base colors, mixing varnishes and tinting colors (especially into colors having a high solids content, “HS colors”), or even more highly pigmented tinting pastes which then constitute the components of the mixing system.
• the matching of the desired hue and hence the mixing of the color components can be effected visually via a system of color cards in a very large number of hue gradations which are based on color standards, such as RAL, BS and NCS, or preferably under computer control, whereby an unlimited number of hues become accessible (“computer color matching”).
• a solid pigment preparation which is in accordance with the present invention was produced by following conventional processes, and comprises the following constituents, each based on the total weight of the preparation:
• Alkyd-melamine baking finish (35% by weight solids content, xylene as solvent), white reduction with white pigment content of 20.0% by weight (TiO 2 , Kronos 2059) (EPL test binder, BASF)

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